Process for finishing cellulosic textile materials with etherified melamines

ABSTRACT

This invention relates to new and etherified methylolated melamines and their use on cellulosic textile materials dyed with direct dyes. The new etherified melamines impart creaseresistance to such materials and the light-fastness of the direct dyes is improved.

United States Patent Inventors Michael Thomas Beachem Somerset; Frederic IIoughton Megson, Martinsville, both 01 NJ.

App]. No. 31,055

Filed Apr. 6, 1970 Division ofser. No. 622,300 Mar. 13, 1967, Pat. No. 3,519,625 N6v.2, 1971 American Cyanamid Company Stamford, Conn.

Patented Assignee PROCESS FOR FINISHING CELLULOSIC TEXTILE MATERIALS WITH ETHERIFIED MELAMINES 5 Claims, No Drawings US. Cl 8/74, 8/116.2, 8/1 16.3, 8/1 15.7, 8/17, 8/21 Int. Cl D061) 5/06, D06m 13/38 Primary Examiner-George F. Lesmes Assistant Examiner-J. Cannon Atmmey-J0hn E. I-lanrahan ABSTRACT: This invention relates to new and etherified methylolated melamines and their use on cellulosic textile materials dyed with direct dyes. The new etherified melamines impart crease-resistance to such materials and the light-fastness of the direct dyes is improved.

PROCESS FOR FINISHING CELLULOSIC TEXTILE MATERIALS WITH ETHERIFIED MELAMINES This invention relates to new compounds and to textile finishes for dyed cellulosic textile materials. More particularly 5 (alky1-OCH:)2

it relates to etherified melamine-formaldehyde precondensates and their use on cellulosic textile materials dyed with direct dyes. Still more particularly, it relates to the use of new etherfied methylolated melamines of the formula III (CH O-alkylh N (Mi o-alkyleconomically and efficiently without adversely affecting many of the other desirable properties of cellulosics, such as for example, fabric hand, soil resistance or fabric durability. However, arninoplast resins do in some cases have an adverse'effeet on color stability of dyed cellulosics. Thus, it is wellknown that aminoplast crease-preventing finishes can cause accelerated fading of many directdyes, i.e., the lightfastness of cellulosic textile material dyed with direct dyes is often reduced when the dyed material is after-treated with an aminoplast resin or reactant, such as urea-formaldehyde or a melamine-formaldehyde condensate. Commercial resins which have been shown to cause fading of certain direct dyes include hexa(methoxymethyl)melamine, polymethylolurea with slight degree of methylation, blends of partially methylated hexamethylolmelamine and urea-formaldehyde reaction products, and methylated trimethylolmelamine In view of the widespread use of both direct dyes and I aminoplast resins on cellulosics, it is extremely undesirable to have the use of the resin for its purpose, restrict the functioning of the dye for its purpose. It is therefore an object of the present invention to provide a means of treating direct-dyed cellulosics with aminoplast resins whereby crease-resistance is imparted to the cellulosic with no substantial reduction in lightfastnesslt is a further object to provide cellulosics which have been direct dyed-and have improved lightfastness, while also exhibiting good crease-resistance by' virtue of treatment 1 with a particular aminoplast resin textile improving agent. 1 Other objects will be apparent from the ensuing description of this invention.

It has now been discovered in accordance with this inven- 'tion that etherified methylolated melamines of Formula 1 im part crease-resistant properties to cellulosic textile materials without adversely affecting the lightfastness of such material dyed with direct dyes. This is surprising discovery'since cellu losics dyed with direct dyes are normally adversely affected as to lightfastness when after-treated with aminoplast textile finishes. The textile finishing aminoplast resins used in this in-. vention are applied to direct-dyed cellulosic textile materials by standard procedures, as by dipping, padding, spraying, etc., and the finishes are converted to an insoluble state by heating the treated fabrics in the presence of a catalyst. The dyed materials thus treated exhibit crease-resistant and wrinklerecovery properties, and a lightfastness equal to, or even better than the untreated, dyed material.

The compounds of Formula I can be made by reacting an N- halomethyl'melamines of Formula 11 with an alkali metal salt of 1 Formula III as follows:

compounds of urn salts of benzyl alcohol, p-methylbenzyl alcohol, p-ethyl- I benzyl alcohol, etc.

The reaction of compounds of Formula II with compounds of Formula III is carried out with or without a solvent, although it is preferable to use a solvent, particularly the alcohol from which the said alkali metal salt is prepared. The reaction is conveniently carried out at room temperature, although any temperature between the freezing and boiling points of the reaction mixture may be used. Equimolar amounts of reactants can be advantageously used, although an excess of either can be present without adverse effect.

The cellulosic textile materials include fibers, threads,

yarns, knitted and woven cloth as well as"nonwoven fabrics and felted materials. These cellulosic materials will normally contain'atleast 50 percent cellulosic fibers, such as cotton, viscose, cupra'mrn'onim rayons, linen, hemp, jute and ramie, either alone or mixed with themselves or other fibers.

The cellulosic textile materials will be dyed with the class of azo dyes known as direct dyes and so classified in the Color Index, second edition. Such dyes are characterized as anionic dyes having affinity for cellulosic fibers when applied from an aqueous dyebath containing an electrolyte. They are mainly azo dyes containing sulfonic acid groups as the sodium salts. Representative direct dyes are Direct Yellow 6(C.l. 4,001),

1, Direct Yellow 1 1 (C.I. 40,000), Direct Orange 26 (C1 29,150), Direct Red 1 (C1. 22,310), Direct Red 31 (C.l.

29,100), Direct Blue 2 (Cl. 22,590) and Direct Green 1 (30,280).

The dyed materials are treated with the textile finishes of this invention using aqueous or organic solvent solutions or dispersions which can be applied by spraying, dipping or padding according to well-known procedures. Between 0.5% and 40% solutions or dispersions are normally used. The amount of finish on the textile material can be varied, usually between 0.5% and 40% based on the weight of the textile material, with amounts between 2.5% and 15% preferably being used for practical crease-resistant and wrinkle-recovery properties. The treated fabrics are dried and then heated, preferably in the presence of a catalyst, to effect insolubility of the precondensate on the fabric (cross-linking, etc. Curing temperatures between 275 and 400 F. for periods of about 20 minutes to 30 seconds are normally used.

Suitable catalysts include those normally used for melamine-formaldehyde condensates and their ethorates. These include the metal salts such as magnesium chloride, zinc nitrate and zinc chloride, ammonium salts such as am- -monium sulfate, ammonium chloride, and organic amino A solution of 39.8 parts (0.101 mole) of N-chloromethyl- N,N',N',N' ,N '-pentakis(methoxymethyl)-2,4,6-triamino-s- CHQOCHS triazine in 54.1 parts (0.50 mole) of benzyl alcohol is added slowly to the reaction mixture of 54.1 parts (0.50 mole) of benzyl alcohol and 2.39 parts (0.105 mole) of sodium at 25-30 C. After a reaction period of about 24 hours, 100 parts of water is added. The organic layer is washed with 10% aqueous sodium hydroxide, sodium chloride solution and a reacted benzyl alcohol is removed by vacuum distillation. The product, a viscous liquid, is N-(benzyloxymethyl)-N,N',N',N" ,N"-pentakis-(methoxymethyl)-2,4,o-triamino-s-triazine. EXAMPLE 2 T w NCmHOz CHaOCzHs 1 (CHaOCHahN- (EH CHa The procedure of example 1 is followed, substituting an equivalent amount of p-methoxybenzyl alcohol for the benzyl alcohol. The product is N-(p-methoxybenzyloxymethyl)- Y N,N',N',N",N"-pentakis(methoxymethyl)-2,4,6-triamino-s- The procedure of example 1 is followed substitutirig E equivalent amount of p-ethylbenzyl alcohol for the benzyl alcohol. The product is N-(p-ethylbenzyloxymethyl)-N,N',N', N",N"-2,4,-triamino-s-triazine.

EXAMPLE 5 Pad baths are prepared containing 0.25% of precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.

Pad bath A N-(Benzyloxymethyl)-N,N',N',N",N"-pentakis(methoxylmethyl)-2,4,6-triamino-s-triazine, the product of example 1, is 85% aqueous dimethylformamide.

Pad bath B N,N,N',N',N",N"-hexakis(methoxymethyl-2,4,6-triaminos-triazine in water, for purposes of comparison.

The pad baths are applied to 80X80 cotton percale at 5% o.w.f. of precondensate solids by standard padding procedure using 80% wet pickup. The treated fabrics are dried for 2 minutes at 225 F. and the finish is cured by heating the fabric at 350 F. for 1.5 minutes.

The wrinkle recovery of the treated fabrics and a sample of untreated fabric is measured on a wrinkle recovery tester following tentative test method 68l959T, described on page B-143 of the 1964 Technical Manual and Year Book of the American Association ofTextile Chemists and Colorists.

The strength loss due to retained chlorine is measured by standard test method 92-1962, described on page B-lOZ of the above reference, before and after five acid rinses.

The acid rinses (acid sours") are carried out by immersing the fabric in an aqueous solution of zinc fluorosilicate followed by drying.

The measurements of Finishes A and 13 corresponding to v 50150 y Volume) mixture of methanol and 131611 The 30 Pad Baths A and B, respectively, show the finishes to be about equivalent in degree of wrinkle recovery, but that Finish A is superior to the other finish in resistance to damage caused by retained chlorine after five acid rinses.

EXAMPLE 6 Pad baths are prepared containing 6.25% precondensate solids and 12% magnesium chloride based on the precondensate solids in the bath.

Pad Bath A N-(Benzyloxymethyl)-N,N,N',N",N"-pentakis(methoxymethyl)-2,4,6-triamino-s-triazine(product of example 1) in acetone. Pad Bath B N,N,N,N',N",N"-hexakis(methoxymethyl)-2,4,6- triamino-s-triazine in water.

The pad baths are applied to a sample of x80 cotton percale dyed with Direct Red 81 (Cl. 28,160) at 5% o.w.f. of precondensate solids by standard padding procedure using 80% wet pickup. The treated fabrics are dried for 2 minutes at 225 F., and the finishes are cured by heating the fabrics at 350 F. for 1.5 minutes. Also a sample of the dyed, but untreated, fabric is rinsed in water and dried. A portion of each of the fabrics of each color in washed in a home-style washing machine at l10-l 15 F. with water containing 0.25% of a commercial anionic surface active agent and b 0.25% of sodium carbonate. The washed fabrics are dried.

Samples of the treated fabrics, both washed and unwashed, are exposed in a Fade-Ometer for 60 hours. The degree of fading of the exposed sampled of fabric is measured as follows:

Spectrophotometric curves of the unexposed portion of dyed fabric and the exposed portion of dyed fabric are recorded for 21 wavelengths over the complete visual range. The spectrophotometric data are converte d t ocolorimetric data by means of a digital computer. Numerical expressions of color in terms of 3-dimensional color coordinates are thus obtained. The two sets of colorimetric data, i.e., one set for unexposed fabric and one set for the exposed fabric, are then converted into a single color difference (in MBS units) by the system of Wyszecki, J. Opt. Sec. Am. 53, 1,318 (1963). The evaluation of the colorimetric data can be done by computer.

The single number color difference thus obtained can be considered in this instance to be strength ratio figures between exposed and unexposed fabric, negative numbers indicating loss in strength, i.e. fading. The larger the color difference It can be seen that Finish A is superior to Finish B in renumber, the greater the difierence in the visual appearance sistance to light-fading and is generally superior to the unbetween the two samples. treated dyed fabric.

It is generally accepted that a color difference of 0.2 NBS We claim: unit is the minimum detectable amount which an experienced 5 l. A process which comprises inpregnating a cellulosic texperson can detect between two samples. The color difference H V m V i "V for an acceptable commercial match is probably between 1.0 and 2.0 NBS units as discussed in the monograph by Judd, Color in Business, Science and Industry," Wiley, New York, 1952. 10

The results of the fading measurements are shown in table I, Finishes A and B corresponding to Pad Baths A and B, respecetherified methylolmelamine C tivel y riz ITT /CHz0alkyl R TABLE] CH),N-C\ /CN\ N CHzOCHr- Fading in NBS Units lnma, washed wherein alkyl" is an alkyl group of l-4 C atoms and R is FinishA -7 o hydrogen, alkyl 1 of up to 18 carbons or lower-alkoxy and Fini h B l2. I .7 heating the impregnated textile material in the presence of a Untreated l0.3 l L3 catalyst to cure the finish to a substantially insoluble state. 2. The process of claim 3 wherein the etherified methylolmelamine is the compound It can be seen that Finish A is superior to Finish B in resistance to light-fading and is generally superior to the un' treated dyed fabric.

Table l, Finishes A and B corresponding to Pad Baths A and IIHCHQO CH3): B, res ectivel C P y \I/ \N OH OCH TABLE 1 (CH;OCHz)zN-C C-N N CIhOCHzCeHs Fading in NBS Units Initial Washed 3. The process of claim 1 wherein the catalyst is magnesium Finish A -7.0 l 1.1 chloride Finish 8 A246 |67 4. The process of claim 1 wherein the textile material is cot- Untreated l0.3 l l.3 ton 5. The textile material produced by the process of claim 1.

tile material bearing a direct dye with a solution of an Patent No.

Dated November 2, 1971 Inventor(s) Michael Thomas Beachem and Frederic Houghton Megson Column 1,

Column 1,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

-- after line 22, please insert a comma the word "hydrogen".

Column 2, lines 8 and 12, the Roman numerals "I" and "II" should read II and III respectively.

Column 2, line 15, please insert the word as after the word are" and before the word "defined".

Column 2, line 72, "ethorates" should read etherates Column 2, line 75, "amino" should read amine Column A, line 2, "0.2595" should read 6.25%

Column line 6, "methoxyl" should read methoxy- Column l, line 54, "in washed" should read is washed Column line 61, "sampled" should read samples Column A, line 70, "MBS" should read NBS Column 6, line 25, "3" should read 1 Signed and sealed this 18th day of April 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Attesting Officer ORM PO-105O {10-69) ROBERT GOTTSCHALK Commissioner of Patents USCOMM-DC BUTTE-P69 U S. GOVERNMENT PRINTING OFFICE 1969 366-330 

2. The process of claim 3 wherein the etherified methylolmelamine is the compound
 3. The process of claim 1 wherein the catalyst is magnesium chloride.
 4. The process of claim 1 wherein the textile material is cotton
 5. The textile material produced by the process of claim
 1. 